Production of halohydrocarbyloxysym-triazines



United States Patent 3,397,204 PRUDUCTION 0F HALOHYDRUCAREYLOXY-SYM-TRIAZINES Van R. Gaertner, Ballwin, Mm, assignor to Monsanto'Company, St. Louis, Mo., a corporation of Delaware No Drawing.Continuation-impart 0tappiication Ser. No. 192,986, May 7, 1962. Thisapplication Oct. 21, N65, Ser. No. 5ilt),343

5 Claims. (Cl. 260 248) ABSTRACT OF THE DISfiLOSURE A process forpreparing (halohydrocaroyloxy)-sym-triazines particularly useful assizing agents for paper and textile waterproofing agents comprisingreacting an epoxide or ether or thioether epoxide with a cyanuryl halideand recovering the resulting (halohydrocarbyloxy)- syrn-triazine havinghalogen atoms bonded to the ring carbon atoms. Friedel-Crafts catalystare useful in a process. A suitable temperature range is 25 to 150degrees centigrade for the reaction period.

This application is a continuation-in-part of copending application Ser.No. 192,986, filed May 7, 1962, now US. Patent No. 3,314,325 issued Oct.26, 1965.

This invention relates to organic ring compounds containing nitrogen andchlorine, and more particularly provides a process for preparinghalogenated symmetrical triazine compounds with halogen-containinghydrocarbon and halogen-containing hydrocarbon ether groups assubstituents therein.

An object of this invention is to provide a method for preparing(halohydrocarbonyloxy)-sym-triazines having halogen atoms bonded to thering carbon atoms.

Other objects, advantages, and aspects of this invention will appearfrom the description hereinafter.

According to this invention there is provided a process for preparingnew compounds having a general formula selected from the groupconsisting of wherein R is selected from the group consisting ofhydrogen, alkyl radicals having from 1 to 22 carbon atoms, aryl radicalshaving from 6 to 12 carbon atoms, and aralkyl and alkaryl radicalshaving from 7 to 24 carbon atoms; Y is a chalcogen element having anatomic weight from 16 to 33, i.e., oxygen or sulfur, R is selected fromthe group consisting of alkyl radicals of from 1 to 22 carbon atoms,aryl radicals having 6 to 12 carbon atoms, and alkaryl radicals andaralkyl radicals having from 7 to 24 carbon atoms, X is a halogen,preferably chlorine or bromine; Z is selected from the group consistingof X, and the radical OOHz l3HR wherein X and R are as above defined; Zis selected from the group consisting of X and the radical wherein X, Yand R are as above defined.

3,397,204 Patented Aug. 13, 1968 See The preferred compounds prepared bythe process of this invention are those having one radical of the typeattached to one of the carbon atoms of the symmetrical triazine ring.The number of such radicals on the carbon atoms of the triazine ring canbe varied from one to two so that when there is present only one suchradical bonded to carbon there will be a halogen atom linked to each ofthe remaining 2 carbon atoms of the triazine ring. Likewise, when twosuch radicals are linked to the carbon atoms of the triazine ring therewill be one halogen atom linked to the remaining carbon atom of thetriazine ring. In preparing the halohydrocarbyloxy halogen-substitutedsymmetrical triazines a cyanuryl halide, that is, a compound of the.formula wherein X is as above defined, is reacted with an epoxide havinga formula selected from the group consisting of wherein R, R, and Y areas above defined, in sufficient quantity to replace at least one but notmore than 2 of the hydrogen atoms linked to the carbon atoms of thetriazine ring with the respective halohydrocarbyloxy-l radicals derivedfrom the respective epoxides used. For example by reacting2,4,6-trichloro-sym-triazine with sufficient propylene oxide to reactwith and replace one chlorine atom, there is obtained as product,2,4-dichloro-6-(2-chloropropoxy)-sym-triazine. Similarly by reacting2,4,6-tribromo-sym-tn'azine with 1 molar equivalent of3-octadecyloxy-1,2-epoxypropane there is obtained as product2,4-dibromo-6(2-chloro -3 octadecyloxypropoxy)-symtriazine.

In preparing compounds of the type described above the cyanuryl halideis reacted with a suificient amount of an epoxide to replace from 1 to 2halogen atoms from the carbon atoms of the triazine ring; preferably onthe average of one such halogen is replaced by reaction with the epoxidewhen the compounds are intended for use in reactive sizing compositions,that is, in sizing compositions wherein the active ingredient of saidcomposition chemically reacts with the substrate to impart sizingqualities thereto and become a part of the substrates chemicalstructure.

It is also within the scope of this invention to replace two halogenatoms in the trihalo-sym-triazine with two different halohydrocarbyloxylradicals by replacing the halogens one at a time, as above, with twodiflerent epoxide reactants. Thus by following the route indicated inthe above paragraph and replacing one halogen atom by reacting one moleof an epoxide with one mole of the trihalo-sym-triazine, and then addingan additional mole of a different epoxide compound to replace a secondhalogen atom, the reaction products can be varied extensively. Forexample by reacting 2,4,6-trichloro-sym-triazine with one mole of1,2-butylene oxide until reaction is complete, and then with 1 mole ofepichlorohydrin, 2- chloro-4-(2-chlorobutoxy)-6(2,3-dichloropropoxy)symtriazine can be obtained.

Examples of cyanuryl halide reactants, that is, halogenatedsym-triazines which can be used in the process of 3 this invention are,for example, 2,4,6-trichloro-sym-triazine, 2,4,6-tribromo-sym-triazine,and mixed chloro-bromo-sym-triazines such as2-chloro-4,6-dibromo-sym-triazine.

One type of epoxide that may be used in the process of this invention isa glycidyl ether of the formula wherein R and Y are as above defined.Examples of such compounds are those wherein R is an alkyl, aryl,alkaryl or aralkyl radical having a total of up to 24 carbon atoms ineither a straight chain or branch chain arrangement. Illustrativeexamples of some alkyl radicals include the methyl, ethyl, propyl,isopropyl, butyl, amyl, hexyl, Z-methylhexyl, heptyl, octyl,Z-ethylhexyl, isononyl, n-dodecyl, tert-dodecyl, 2-propylheptyl,S-ethylnonyl, 2- butyloctyl, n-tetradecyl, n-pentadecyl, tertoctadecyl,eicosyl, docosyl, tetracosyl, 2,6,8-trimethylnonyl, and 7-ethyl-2-methyl-4-undecyl radicals. An especially valuable class of alkylradical is that derived from an olefin monomer, dimer, trimer, tetramer,pentamer or the like, carbon monoxide, and hydrogen according to the oxoprocess. Such alkyl radicals include branch-chained tridecyl radicalsfrom propylene tetramer or butylene trimer, the branch-chain decylradicals derived from propylene trimer, the branch-chained hexadecylradicals derived from propylene pentamer, and the branch-chained nonylradical derived from diisobutylene. Aryl radicals include phenyl, tolyl,naphthyl, biphenylyl, etc. The alkaryl radicals can include themonoalkylated as well as the polyalkylated aryl radicals. The monocyclicand dicyclic aryl radicals are preferred. Illustrative examples of someradicals which can be used include tolyl, benzyl, dimethylphenyl,Z-phenylethyl, propylphenyl, tert-octylphenyl, naphthylmethyl,amylphenol, heptylphenyl, nonylphenyl, 2 ethylheptylphenyl, decylphenyl,4-tert-dodecylphenyl, 2 tridecylphenyl, 3-tert-octadecylphenyl,2-nonyl-l-naphthyl, beta- 1-(2-butyl0ctyl)-2-naphthyl, 3-butylphenyl,and 2,4-dinonylphenyl radicals.

Illustrative examples of some glycidyl ethers which can be used as theether reactants in the process of this invention are as follows:

3-methoxy-1,2-epoxypropane 3-prop oxy- 1 ,2-epoxypropane3-hexyloxy-1,Z-epoxypropane 3 -heptyloxy-1,2-epoxypropane 3-decyloxy-1,2-epoxypropane 3-(dimethy1phenoxy) l,2-epoxypropane 3-(tert-octadecyloxy) -l,2-epoxypropane 3- (nonylphenoxy) -l,2-epoxypropane 3- (2-propylheptyloxy) 1,2-epoxypropane 3-(n-hexadecyloxy)-1,2-epoxypropane 3 2,4dino nylphenoxy) 4 l ,2-epoxyprpane 3-(n-octadecyloxy) -1 ,2-epoxypropane 3 (decylphenoxy) -1,2-epoxypropane 3tridecyloxy) -1,2-epoxypropane 3- 2-nonyl-1-naphthoxy) -1,2-epoxypropaneIllustrative examples of some of the glycidyl thioethers which can beused as the ether reactant in the process of this invention are asfollows:

3-methylthio-1,2-epoxypropane 3-ethylthio-1,2-epoxypropane 3-butylthio-1 ,Z-epoxypropane 3-octylthio-1,2-epoxypropane 3-nonylthio-1,2-epoxypropane 3- (n-hexadecylthio) -1 ,Z-epoxypropane 3-(2,4-dinonylphenylthio) -1,2-epoxypropane 3- (n-octadecylthio) -1,2-epoxypropane 3- 2-butyloctylthio 1 ,2-ep oxypropane 3- (tridecylthio)1,2-epoxypropane 3- (Z-ethylheptyl) phenylthio] -1,2-epoxypropaneS-(n-pentadecylthio) -1,2-epoxypropane 3- (3-butylphenylthio)1,2-epoxypropane The glycidyl ether and thioether reactants used in theprocess of this invention can be readily prepared from the correspondingchlorohydrins, e.g., l-alkoxy-3-chloro-2- propanol,1-alkaryloxy-3-chloro-2-propanol, l-alkylthio- 3-chlor-o-2-propanol, and1-alkarylthio-3-chloro-2-propa- I101. The chlorohydrin isdehydrochlorinated in an aqueous alkaline solution, preferably in thepresence of a lower dialkyl sulfoxide. The chlorohydrin can be readilyprepared from a long-chain alcohol and epichlorohydrin by reactingsubstantially 1 mole each of the alcohol and epichlorohydrin in thepresence of an acid-type catalyst such as boron trifluoride, zincchloride, etc.

Some examples of epoxide or om'rane compounds that are suitable forreaction with the 2,4,6-trihalo-sym-triazine compound are for example,ethylene oxide, and alkyl derivatives thereof such as propylene oxide,isobutylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane,2,3-epoxypentane, 2,3-epoxyhexane, 1,2-epoxyhexane, 1,2- epoxyheptane,2,3-epoxy-3-ethylpentane, 1,2 epoxy 4- mcthylpentane,1,2-epoxy-2-ethylhexane, l,2-epoxy-2,4- trimethylpentane,1,2-epoxy-2,3-dimethylheptane; haloalkyl-substituted alkylene oxidessuch as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin,1,2- epoxy-4-bromobutane, 2,3-epoxy 4 bromobutane, 1,2-

. epoxy-3,4dibromobutane, 2,3-epoxy-l-bromopentane, 3,4-

epoxy-Z-chlorohexane, 1,2 epoxy-3,3,3-trifluoropropane; thealkenyl-substituted oxide rings such as 3,4-epoxy-4- methyl-l-pente'ne,1,2-epoxy-3-butene and 3,4-epoxy-lbutene; aryl-substituted alkyleneoxide rings such as (epoxyethyl benzene, (1,2-epoxyl -methylethylbenzene, (3-chloro-1,2-epoxypropyl)benzene; 1,2 epoxytridecane,1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctodecane,1,2-epoxyeicosane, 1,2-epoxy-3-cyclohexylpropane,1,2-epoxy-3-cyclobutylpropane, 1,2-epoxy-4-(4-noctyl-3-cyclohexenyl)butane, 1,2 -epoxyhenecosane, 1,2-epoxydocosane, 1,2-epoxytetracosane, 1,2-epoxypentacosane, and1,2-epoxyhexacosane.

Examples of products obtained by reacting a cyanuryl trihalide with oneof the above identified expoxide compounds to replace one halogen atomin the triazine ring are:

2,4-dibromo-6-(2,3-dichloropropoxy)-sym triazine obtained by reacting2,4,6-tri bromo-sym-triazine with epichlorohydrin;

2,4-dichloro-6-(2-chloroethoxy)-sym-triazine obtained by reacting2,4,6-trich1oro-sym-triazine with ethylene oxide;

2,4-dibromo-6-(2-bromo6ctyloxy)-sym-triazine obtained by reacting2,4,6-tribromo-sym-triazine with 1,2-epoxy- Octane;

2,4-dichloro-6(2-chloro6ctadecyloxy)-sym triazine obtained by reacting2,4,6-trichloro-sym-triazine with 1,2- epoxyoctadecane;

2,4-dibromo-6-(2-bromodocosyloxy) sym triazine obtained by reacting2,4,6-tribromo-sym-triazine with 1,2- epoxydocosane;

2,4-dichloro-6-(2-chloro-2-phenylethoxy) -sym-triazine obtained byreacting 2,4,6-trichloro-sym triazine with epoxyethylbenzene;

2,4-dibromo-6-(2-bromo-3-naphthylpropoxy)-sym-triazine obtained byreacting 2,4,6-tribromo-syrn-triazine with 1,2-epoxy-3-naphthylpropane;and

2,4-dichloro-6-(2-chloro-3 biphenylylpropoxy)-sym triazine obtained byreacting 2,4,6-trichloro-sym-triazine withl,2-epoxy-3-biphenylylpropane.

Examples of products obtained by reacting a trihalosym-triazine with asuflicient amount of an epoxide to react with and replace two halogenatoms therefrom are:

2-chloro-4,6-bis(2-chloropropoxy)-sym triazine obtained by reacting2,4,6-trichlorosym-triazine with 1,2-epoxypropane;

2-'bromo-4,6-bis(2-bromododecyloxy)-sym triazine obtained by reacting2,4,6-tribromo-sym-triazine with 1,2- epoxydodecane;

2-chloro-4,6-bis(2-chloro6otadecyloxy)-sym triazine obtained by reacting2,4,6-trichloro-sym-triazine with 1,2-

epoxyoctadecane; and 2-bromo-4,6-bis(2-bromotetracosyloxy)-sym-triazineobtained by reacting 2,4,6-tribromo-sym-triazine with 1,2-

epoxytetracosane.

Examples of products obtained by reacting a 2,4,6-trihalo-sym-triazinewith a glycidyl ether include:2,4-dichloro-6-(2-chloro-3-ethoxypropoxy)-sym triazine obtained byreacting 2,4,6-trichloro-sym-triazine with l,

2-epoxy-3-ethoxypropane; 2,4-dibromo-6-(2-bromo-3-hexadecyloxypropoxy)symtriazine obtained by reacting 2,4,6-tribromo-sym-tria- Zine with1,2-epoxy-3-hexadecyloxypropane;2,4-dichloro-6-(2-chloro-3-phenoxypropoxy)-sym-triazine obtained byreacting 2,4,6-trichloro-sym-triazine with 1,2-epoxy-3-phenoxypropane;

2-bromo-4,6-bis(2-bromo-3-tricosyloxypropoxy)-sym-triazine obtained byreacting 2,4,6-tribromo-sym-triazine with1,2-epoxy-3-tricosyloxypropane;

2-chloro-4,6-bis 2-chloro-3 -iso pro poxypropoxy) sym-triazine obtainedby reacting 2,4,6-trichloro-sym-triazine with1,2-epoxy-3-isopropoxypropane; and

2-chloro-4,6-bis(2-bromo-3 naphthyloxypropoxy) symtriazine obtained byreacting 2-chloro-4,6-dibromo-symtriazine with l,2-epoXy-3-naphthyloxypropane.

As above indicated, it is within the realm of this invention to preparederivatives of halotriazine compounds in which a differenthalohydrocarbyloxy group is attached to each of two carbon atoms of thetriazine ring so substituted. Examples of such compounds are:

2-chloro-4-(2-chloro-3-bromopro-p-oxy)-6(2 chloro 3-phenoxypropoxy)-sym-triazine obtained by reacting 2,4,6-trichloro-sym-triazine with epibromohydrin and then with1,2-epoxy-3-phenoxypropane;

2-bromo-4- (Z-bromo'cictadecyloxy -6- Z-bromopropoxy sym-triazineobtained by reacting 2,4,6-tribromo-symtriazine with 1,2-epoxyoctadecaneand then with propylene oxide; and

2-chloro-4-(Z-chloro-Z-ethylhexyloxy)-6-(2 chloro 3-hexyloxypropoxy)-sym-triazine obtained by reacting 2,4,6-trichloro-sym-triazine with 1,2-epoxy-2-ethylhexane and then with1,2-epoxy-3-hexyloxypropane.

The halohydrocarbyloxyl symmetrical triazine compounds of the abovedefined types having 1 or 2 halogen atoms still attached to the carbonatoms of the triazine ring are recovered as such and used in sizingcompositions.

The reaction of the epoxyalkane or glycidyl ether reactant with thecyanuryl trichloride or tribromide takes place readily by contactingeither reactant with the cyanuryl trihalide in an appropriate solvent ordiluent which will not react with either of the reactants and is a goodsolvent for both, advantageously in the presence of a catalyst, and thenstirring the resulting reaction mixture until the desired product hasbeen formed. Although reaction may take place slowly at temperatures aslow as 25 C., ordinarily a temperature of about 50 to 80 C. is used tocarry out the reaction. Preferably the temperature is maintained below150 C. and usually below 125 C. since the more elevated temperaturesappear to cause decomposition of the products. Any solvent or diluentwhich has a convenient boiling point at the temperature of re action andwhich will not react with either of the reactants can be used. Suchsolvents or diluents are for example acetonitrile, tetrahydrafuran,dioxane, ether, and hydrocarbon solvents such as xylene, toluene,hexane, and the like.

Ordinarily, the reaction of this invention is conducted at atmosphericpressures while superatmospheric pressures can be used and in fact, maybe necessary in systems where-in lower molecular weight epoxidecompounds are used.

The epoxyalkane orthe glycidyl ether reactants and the cyanuryltrihalide reactants are preferably reacted in approximatelystoichiometric proportions; however, care is taken to insure that notmore than 2 molar equivalents of the epoxyalkane or glycidyl etherreactant is used per mole of the cyanuryl trihalide reactant since it isdesirable to leave at least one and preferably two halogen atoms bondedto the carbon atoms of the triazine nucleus when the products are to beused in sizing compositions.

The reaction of the epoxyalkane or the glycidyl ether reactant with thecyanuryl trihalide is primarily an addition type reaction resulting inthe formation of a single product. The substituted halotriazine productis usually recovered from the reaction mixture by first removing theunconverted reactants and by-products by distillation under reducedpressure, filtration, solvent extraction, etc. and then purifying theresidue. Conventional purification techniques including serialredissolving the residue in the solvent, decolorizing the mixture withcharcoal, filtering the mixture, and allowing the product to crystallizeor aspirating oif the solvent and possibly distilling the product invacuo.

The epoxy compounds and the glycidyl ethers react with the cyanuryltrihalide reactants with comparative ease. The mixture is usually heatedto a higher temperature on the order of to 130 C. to insure completereaction, but such heating is not necessary where it is evident by wellknown chemical means that the reaction is complete. The higher reactiontemperatures are generally used to promote reaction of materials ofhigher molecular weight.

The reaction of the epoxyalkane and glycidyl ether reactants with thecyanuryl trihalide reactants is generally conducted in the presence ofan appropriate catalyst. The use of catalyst is preferred in thatreaction time is thereby substantially decreased, use of a lowerreaction temperature is facilitated, and yields of the desired productare materially improved. As catalyst there may be employed suchcompounds as FriedelCrafts catalysts, e.g., titanium tetrachloride,zirconium tetrachloride, aluminum chloride, ferric chloride, borontrifluoride, tin tetrachloride, magnesium chloride, and zinc chloride.How ever, the reaction does proceed slowly without a catalyst. Zincchloride and ferric chloride are preferred catalysts.

The compounds of the present invention are stable, usually high boilingmaterials which range from viscid liquids to waxy or crystalline solids.They are particularly valuable as an essential active ingredient inpaper treating compositions for treating of paper products which includecardboard and other thicker papers made from one or more plies of paperstock. They are also active as biological toxicants, particularly asherbicides.

The compounds prepared by the process of this invention havinghalohydrocarbyloxyl substituents having from 12 to 28 carbon atoms areuseful as sizing agents for textiles, etc., but are particularlyvaluable as such for paper sizes since the substituted halotriazinecompounds have pronounced hydrophobic properties. It is preferred forthe application of these materials to fibrous products such as textiles,paper and paper pulp to utilize dispersing agents or wetting agentswhich may have the additional property of remaining in solution in thewater without being absorbed by the fiber at least to a considerableextent during application.

The invention is further illustrated by but not limited to the followingspecific examples.

EXAMPLE 1 To 32.7 g. (0.10 mole) of n-octadecyl glycidyl ether there wasadded 27.6 g. (0.15 mole) of cyanuryl chloride in 50 ml. ofacetonitrile. The mixture was stirred and heated to reflux (about C.),and then about 0.5 g. of zinc chloride was added. The mixture was heatedand stirred for 20.5 hours. Acetonitrile was removed under aspiratorvacuum to about C. The residue was cooled to room temperature and then100 ml. of hexane was added, with stirring. The excess unreactedcyanuryl chloride (9.0 g.) and zinc chloride were filtered 011. Thefiltrate was heated to 110 C. under aspirator vacuum to remove hexane,leaving a light orange oil. The light orange oil product was purified byremoval by sublimation of additional cyanuryl chloride, and redissolvingthe residue in hexane, treating it with decolorizing charcoal, filteringoff the charcoal, and aspirating off the hexane as before, to leave asresidue 31.2 g. of 2,4-dichlro-6-(2-chloro-3-octadecyloxypropoxy)-s-triazine, which analyzed ascontaining 7.75% nitrogen as compared with 8.22% nitrogen, thecalculated value.

EXAMPLE 2 In a 300 ml. bomb reactor there were placed 36.9 g. (0.20mole) of cyanuryl chloride and 0.5 g. of zinc chloride with ml. ofacetonitrile containing 17.5 g. (0.3 mole) of propylene oxide. The bombwas sealed and heated and rocked for approximately 12 hours at C. Thebomb reactor was emptied, the contents filtered, and then aspirated toremove acetonitrile. The residue was distilled giving 21.5 g. of2,4-dichloro-6-(2- chloropropoxy)-s-triazine; 11 1.5256.

The above reaction was also run at atmospheric pres sure to give2,4-dichloro-6-(2-chloropropoxy)-sym-triazine, B.P. 114118 C./0.2 mm., n1.5297, analyzing as containing 30.43% carbon, 2.80% hydrogen, 17.28%nitrogen, and 43.43% chlorine as compared with 29.7% carbon, 2.50%hydrogen, 17.33% nitrogen, and 43.8% chlorine, the calculated values forC H CI N O.

To 15.3 g. of 2-(2-chloropropoxy)-4,6-dichloro-symtriazine in benzenethere was added sodium methoxide in methanol (7.0 g. of sodium methoxidein 35 m1. of methanol) to convert the product to trimethyl cyanurate;distillation gave propylene oxide as solution which was collected andanalyzed for oxirane content, which indicated that 12.7% yield wasisolated.

The benzene was distilled ofi leaving a slurry which was cooled,filtered, and washed three times with water. Recrystallization fromwater gave long needle-like crystals, M.P. 133.5135 C. The melting pointof the trimethyl cyanurate was identical to the melting point oftrimethyl cyanurate prepared by another method. The melting point of amixture of the two products was the same, i.e., 133.5 to C.

EXAMPLE 3 To 210 ml. of a solution of 36.9 g. of cyanuryl chloride inacetonitrile stirred at 70 under a Dry Ice condenser there was addedethylene oxide entrained in a stream of nitrogen. When 12.8 g. ofethylene oxide had been added,

the temperature was 69 in the boiling mixture. When little [reactionoccurred in 30 min., about 0.1 g. anhydrous zinc chloride was added, andafter another 30 min., 0.1 g. anhydrous ferric chloride was added andheating under reflux continued for twenty hours. The solution wasconcentrated by distillation and the solvent replaced with carbontetrachloride, from which a total of 24.6 g.(67% recovery) of cyanurylchloride crystallized in three crops.

The material remaining in solution was distilled in vacuo and the lowerboiling material redistilled, mainly at 102104/ 0.1 mm. n 1.5404.Analysis showed it to contain 26.78% carbon, 2.09% hydrogen, 17.78%nitrogen and 47.51% chlorine compared to the values calculated for2,4-dichloro-6-(2-chloroethoxy)-sym-triazine of 26.3% carbon, 1.76%hydrogen, 18.4% nitrogen and 46.5% chlorine.

From the first distillation, a fraction boiling at 134- (dec.3/0.30.5mm. crystallized and recrystallization from dioxane and then three timesfrom carbon tetrachloride gave colorless crystals, M.P. 109.5111containing 33.51% carbon, 3.16% hydrogen, 22.11% nitrogen, and 28.04%chlorine corresponding to 33.5% carbon, 3.21% hydrogen, 22.3% nitrogenand 28.3% chlorine calculated for C H Cl N O Thesubstituted-halo-sym-triazines are particularly useful as sizing agentsfor paper, but are also good water proofing agents for cotton and othertextiles.

What is claimed is:

1. A method which comprises contacting and reacting a2,4,6-trihalo-sym-trianine having the halogen atoms selected from thegroup consisting of chlorine and bromine with an epoxide compound havinga formula selected firom the group consisting of Boston, and RYCH;CHCH;

wherein R is selected from the group consisting of hydrogen, alkylradicals having from 1 to 22 carbon atoms, aryl radicals having from 6to 12 carbon atoms; and alkairyl and aralkyl radicals having from 7 to24 carbon atoms; Y is a chalcogen element having an atomic weight ofiirom 16 to 33; and R is selected from the group consisting of alkylradicals having from 1 to 22 carbon atoms, aryl radicals having 6 to 12carbon atoms, and alkaryl and aralkyl radicals having from 7 to 24carbon atoms in the presence of a catalytic amount of "a Friedel-Ciraftscatalyst, and recovering firom the resulting reaction mixture a compoundhaving a formula selected from the group consisting of wherein R and Rare as defined above, X is selected from the group consisting of bromineand chlorine; Z is selected from the group consisting of X and theradical 0oH1( JHR and Z is selected from the group consisting of X andthe radical -o CHn JHGHF-Y-R' wherein R, X, and Y are as defined above.

2. A method according to claim 1 wherein the 2,4,6- trihalo-sym-triazineis cyanuryl chloride, and the epoxide compound has the formula whereinthe alkyl radical has from 1 to 22 carbon atoms, and recovering from theresulting reaction mixture a compound of the formula 0 CHzOllEl-alkylCl-i'1\ -Cl N/ wherein alkyl is as defined above.

3. A method according to claim 1 wherein the 2,4,6- trihalo-sym-tniazineis cyanuryl chloride and the epoxide compound has the formulaalkyl-O-CILCHCH:

wherein the alkyl radical has from 1 to 22 carbon atoms, and recoveringfrom the resulting reaction mixture a compound having the formulawherein alkyl is as defined above.

4. A method which comprises contacting and reacting cyanuryl chloridewith propylene oxide in the presence of a catalytic amount of zincchloride, and recovering from the resulting reaction mixture2,4-dichloro-6-(2-chloropropoxy)-sym-triazine.

5. A method which comprises contacting and reacting 'cyanuryl chloridewith 1,2-epoXy-3-octadecyloxypropane in the presence of a catalyticamount of the zinc chloride, and recovering from the resulting reactionmixture 2,4-

10 dichloro 6 (2=ehloro-3-octadecyloxypropoxy)-syrn-t1ritazine.

References Cited UNITED STATES PATENTS 3,214,325 10/1965 Gaertner260--248 HENRY R. JILES, Primary Examiner.

J. M. FORD, Assistant Examiner.

